CN1166815C - Electrogalvanized steel sheet with light tone - Google Patents
Electrogalvanized steel sheet with light tone Download PDFInfo
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- CN1166815C CN1166815C CNB971125732A CN97112573A CN1166815C CN 1166815 C CN1166815 C CN 1166815C CN B971125732 A CNB971125732 A CN B971125732A CN 97112573 A CN97112573 A CN 97112573A CN 1166815 C CN1166815 C CN 1166815C
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/22—Electroplating: Baths therefor from solutions of zinc
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
- C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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- Mechanical Engineering (AREA)
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- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
An electrogalvanized steel sheet with a light tone having an electrogalvanized coating layer formed on one side or both sides of a steel sheet. In the electrogalvanized steel sheet, the orientation indices of the (00.2) plane and the (10.1) plane of electrogalvanized coating layer are 1.0 or greater and 1.0 or less, respectively and at the same time, (1) the orientation index of the (10.3) plane is 2.0 or greater; or (2) a ratio of [the sum of the orientation indices of the (0.02) and (10.3) planes] to [the orientation index of the (10.1) plane] is 4.5 or greater. The orientation index of each crystal plane of electrogalvanized coating layer satisfies the following equations: A=[Ico(00.2) + Ico(00.4) + Ico(10.3)] >= 8.0; B=[Ico(10.0) + Ico(10.1) + Ico(10.2) + Ico(11.0)] <= 1.0, supposing that Ico(hk.1) represents the orientation index of a (hk.1) crystal plane.
Description
Technical field
The present invention relates to a kind of electrogalvanizing steel plate that glossy surface is arranged, the steel plate of this electro-galvanizing is very useful as the steel plate galvanized that can use, it is used for the outside sheet material of automobile, household electrical appliance, office automation equipment or material of construction without external coating (EC).
Background technology
Thereby electrogalvanizing steel plate is because its fabulous erosion resistance and appearance surfaces are used for as automobile its industrialization, the outside board-like material of household electrical appliance or office automation equipment and material of construction.
Because electrogalvanizing steel plate has fabulous erosion resistance, they are mainly used on undercoat plate and their surface and cover external coating (EC), therefore need not to pay special attention to the outside surface performance on dope layer surface.Yet recently, the user has quickened to omit or simplify the process of external coating (EC) step for the purpose of simplifying step and reduce cost, and trends towards using the electrogalvanizing steel plate which is provided with coating.In this case, after the surface of electrogalvanizing steel plate being carried out various transparent chemical transformation such as the organic or inorganic film coating processing processing of handling or approaching as chromate coating, use it not have the surface of external coating (EC), thereby improve its erosion resistance more and give its formability simultaneously, anti-impression of the hand, lubrication, weldability, the performance of conductivity and the like.
Under such trend, the surface of the outward appearance of electrogalvanizing steel plate is basically as the appearance surfaces of end product, so the appearance property of the steel plate tool that becomes has very important significance.
Luminosity among the various outside surface performances of steel plate galvanized, brighter light is tangible optimal selection, so the user can strengthen along with the increase of rigidity for the special demands than the light degree.
Under these circumstances, proposed to make the certain methods of the electrogalvanizing steel plate of being with brightness.For example, Japanese patent application HEI5-36514 number, it has been described by can obtain electro-galvanizing and the chromate coating steel plate with brightness to the orientation of specifying specific crystal face in electric galvanizing coating, particularly, by respectively (00.2) plane and (10.1) planar orientation index being controlled at 0.5 or more and 1.0 or some realize top requirement less.
Japanese patent application HEI7-11071 number, similar with above description, disclosed in electric galvanizing coating the orientation of special crystal face, more particularly, be equal to or greater than 1.0 and be equal to or less than 1.0 by control (10.3) plane and (10.1) planar orientation index respectively; Perhaps by control (11.0) plane and (10.1) planar orientation index respectively for be equal to, or greater than 0.6 be equal to or less than 1.0; Maybe control (00.2) planar orientation index is equal to or less than the 1.0 electro-galvanizing chromiumcoating steel plates that all can obtain brightness when satisfying any one of orientation index described above.
Those methods of describing in the above document are based on the technology of the brightness that improves coatingsurface by the orientation of specifying specific crystal face in electric galvanizing coating.Even they are characterised in that coatingsurface is subjected to as chromate coating, and the chemical transformation that adds optional transparent organic film coating is thereon handled, also the reduction of luminosity can be suppressed to greatest extent, therefore, can obtain a kind of electrogalvanizing steel plate with brightness.In above document, described " brightness (L value) is not less than 55 " belongs to the standard of " a kind of luminosity " and steel plate galvanized that this standard is satisfied in estimation can sufficiently satisfy the demand of user to brightness as sheet material.
The inventor has carried out extensive investigations and has found that luminosity (brightness) as the electro-galvanized layer described in the top document is subjected to the influence of the orientation of its specific crystal face really, but neither usually can be by designated orientations to obtain stable luminosity.Therefore, can not be satisfactory from the above method of viewpoint of reliability.In addition, under existing conditions, the user to the level of brightness have relatively high expectations and the standard of " brightness is not less than 55 " can not satisfy user's demand.Or rather, without any the electrogalvanizing steel plate that other coating is handled, the high level of brightness is not less than 80, even and be not less than 75 and be not less than 70 become a kind of demand after thin transparent film processing after chromate coating is handled.Each brightness is all represented with L.
Summary of the invention
Above-mentioned viewpoint can be finished the present invention.The object of the present invention is to provide a kind of electrogalvanizing steel plate, its luminosity is higher than traditional electrogalvanizing steel plate out and away and can satisfies the high photometric requirement of using the L value representation, even promptly be not less than 80 and after chromate coating is handled, be not less than 75 and after thin transparent film processing, be not less than 70 in the high-level brightness of the electrogalvanizing steel plate of handling without any other coating.
Electrogalvanizing steel plate of the present invention has overcome a difficult problem described above, a kind of one or both sides of steel plate all have the electrogalvanizing steel plate of the band brightness of electric galvanizing coating, it is characterized in that (00.2) plane of described electric galvanizing coating and (10.1) planar orientation index be respectively more than or equal to 1.0 and be less than or equal to 1.0 and simultaneously the ratio of [(00.2) and (10.3) planar orientation index sum] and [(10.1) planar orientation index] be more than or equal to 4.5, and on the described electric galvanizing coating surface formed chromate coating by Cr for being less than or equal to 50mg/m2.
The one or both sides of its steel plate of electrogalvanizing steel plate are formed with electric galvanizing coating, are characterised in that the orientation index of each crystal face of electric galvanizing coating satisfies following relational expression:
A＝[Ico(00.2)+Ico(00.4)+Ico(10.3)]≥8.0
B＝[Ico(10.0)+Ico(10.1)+Ico(10.2)+Ico(11.0)]≤1.0
Suppose Ico (hkl) representative (hkl) planar orientation index.
In the present invention, satisfy " A/B 〉=13.0 " by the orientation index of controlling each crystal face and can obtain electrogalvanizing steel plate than the light degree.
So the electrogalvanizing steel plate that obtains need not just can effectively use owing to its fabulous outside surface in any other coating processing, thereby can be used for outer sheet material, household electrical appliance or the office automation device and the material of construction of automobile.Consider further raising, the actual steel plate that uses after transparent organic or inorganic film coating processing is handled or approached to chromate coating in erosion resistance, formability and anti-impression of the hand performance.Handle and the Cr coating wt need be controlled at 50mg/m for chromate coating
2Or it is less and be controlled to be 2g/m for transparent film coating net weight
2Or still less.
According to the present invention, the housing of electrogalvanizing steel plate just may obtain to be not less than 80 under situation about handling without any other coating, chromate coating is not less than 75 after handling, thin clear films coating is handled and is not less than 70 brightness afterwards, each brightness L value representation that gets by the JISZ8730 measurement.
The present invention has as above described formation, making to provide electrogalvanizing steel plate exhibit high brilliance when it is not handled through any other coating to be not less than 80, after chromate coating is handled, be not less than 75 and the processing of thin transparent film after be not less than 70, each value is based on the L value, also [(00.2) and (10.3) planar orientation index]/[ratio of (10.1) planar orientation index improves a lot the quality of no coating electrogalvanizing steel plate except (00.2) and (10.1) planar orientation index also has by specifying.
In addition, provide be higher than traditional example far away be not less than the electrogalvanizing steel plate of 80 high level luminosity by the L value, be to be divided into two groups by crystal face with electric galvanizing coating, just one group is play a part brightness and another group plays opposite effect to brightness, and determine then respectively by the represented direction index group of aforesaid relational expression A and B and.Except above requirement, also by determining especially to specify (00.2) and (10.1) planar orientation index will bring up to 83 or even higher with the brightness of L value representation in A/B ratio and this external crystal face.This electrogalvanizing steel plate can be used for various outer sheet materials or material of construction.In addition, handle and/or approach the transparent film coating by chromate coating and handle, steel plate has improved its erosion resistance, lubrication, anti-scratch trace, weldability, electroplated coating performance and lacquer tack and it under the situation of the brightness that does not weaken it can be therefore and by practical application.
Description of drawings
Fig. 1 has shown electric galvanizing coating (10.1) and (00.2) planar crystalline orientation synoptic diagram to the influence of the brightness of coatingsurface;
Fig. 2 has shown the synoptic diagram of electric galvanizing coating (10.3) planar orientation index to the influence of the brightness of coatingsurface;
Fig. 3 shown electric galvanizing coating [00.2) and (10.3) planar orientation index and] to the ratio of [(10.1) planar orientation index] synoptic diagram to the influence of electric galvanizing coating surface luminosity;
Fig. 4 shows in the electrogalvanizing steel plate synoptic diagram of the summation of the orientation index that equation A and B with proportionlity represent to the influence of the brightness on electrogalvanizing steel plate surface simply;
Fig. 5 shows the synoptic diagram of the relation of A/B ratio and brightness (L value);
Fig. 6 shows the synoptic diagram of the orientation index of (00.2) and (10.1) to the influence of brightness;
Fig. 7 shows the synoptic diagram of relation of the chromate coating weight of brightness and coatingsurface;
Fig. 8 has shown brightness and forming the relation of thin transparent organic membrane coating to transparent film, coating wt after having plated chromate coating.
Embodiment
By the process of experimental sequence the present invention is described more definitely hereinafter.
The present inventor adopts a kind of general promptly using with the common used in industry production method that the not sulfuric acid salt bath of lysis electrodes is housed.By changing the various of electro-galvanizing such as electrolyte ph, the temperature of groove, current density, flow velocity and plating tank component are carefully studied the relation of the orientation of the luminosity of electrogalvanizing steel plate and coating crystal face.
According to research, the photometric quantity of coatingsurface is evaluated by the brightness value of representing with JISZ 8730 (L value), and the high preferred orientation of coating is calculating according to the diffraction peak in X-ray diffraction by the following method then.
(1) the diffraction peak density of each crystal face that learn to be obtained by X-ray diffraction of electric galvanizing coating is represented with I (hkl).
(2) the standard diffraction peak density meter of each crystal face (hkl) is shown Is (hkl) (adding letter " S " expression standard) under the situation of using the standard zinc powder.
(3) orientation index of each crystal face of electric galvanizing coating is defined as Ico (hkl) (add letter " Co " expression high preferred orientation) and determines above-mentioned value according to following equation.
Ico(hk·l)＝I/Is
Suppose according to claim 1 of the present invention or 2
I＝I(hk·l)/{I(00·2)+I(10·0)+I(10·1)+I(10·2)+
I(10·3)+I(11·0)}
Is＝Is(hk·l)/{Is(00·2)+Is(10·0)+Is(10·1)+
Is (102)+Is (103)+Is (110) } and according to claim 3 of the present invention or 4,
I＝I(hk·l)/{I(00·2)+I(0·04)+I(10·0)+I(10·1)+
I(10·2)+I(10·3)+I(11·0)}
Is＝Is(hk·l)/{Is(00·2)+I(0·04)+Is(10·0)+Is(10·1)
+Is(10·2)+Is(10·3)+Is(11·0)}。
The orientation index Ico (hkl) of the crystal face of electric galvanizing coating represents that this value is obtained divided by the relative density Is of the same crystal face in the zinc powder by the relative diffraction density I of the crystal face of spelter coating, adds correction.
By the way, the numerical value that in ASTM (and JCPD), contains Is described above (hkl).In table 1, be expressed as follows:
Table 1
| Spacing (A) | 2 θ (degree) | (hkl) Miller indices plane | Is (hkl) diffracted intensity |
| 2.475 | 36.26 | (00.2) | 53 |
| 2.309 | 38.97 | (10.0) | 40 |
| 2.092 | 43.21 | (10.1) | 100 |
| 1.686 | 54.36 | (10.2) | 28 |
| 1.342 | 70.04 | (10.3) | 25 |
| 1.332 | 70.69 | (11.0) | 21 |
| 1.237 | 77.02 | (00.4) | 2 |
Relation between the orientation index of the luminosity on the surface of the electric galvanizing coating that obtains like this and each crystal face is studied.The result finds not have clear and definite relation between the orientation index of luminosity and each crystal face, in other words, when the orientation index of a certain crystal face was very big, it is very light or very dark that surface brightness becomes inevitably, thereby can not confirm the definite relation between the orientation index of luminosity and each crystal face.
Therefore the orientation index of each crystal face is not studied, and the relation of the orientation index of brightness and a plurality of crystal faces is studied.
Fig. 1 is a diagram that shows electric galvanizing coating (00.2) and (10.1) planar orientation index to the influence of the brightness of coatingsurface.From figure, can find out significantly, (00.2) planar orientation index be 1.0 or when bigger and (10.1) planar orientation index be 1.0 or fewer the time, some surfaces demonstrate and are not less than 80 high levels of brightness (L value).Yet, in above-mentioned scope, find that the low-level brightness of some planar (L value) is not higher than 65.
According to above result, inferred confirmed two kinds of requirements, promptly be, " (00.2) planar orientation index be controlled at 0.5 or more and (10.1) planar orientation index control to 1.0 or few and " be not enough to obtain to be not less than 80 high level L value.
When above two requirements of hypothesis are met, consider of the influence of the orientation index of other crystal face to luminosity, the planar orientation index except (00.2) and (10.1) plane has been done to scrutinize to the influence of brightness.As a result, the tangible difference of luminosity is as follows:
(1) (10.3) planar orientation index, or
(2) ratio of [(00.2) and (10.3) planar orientation index and] and [(10.1) planar orientation index] and confirmed when (10.3) planar orientation index be 2.0 or more, particularly 2.5 or more, or above ratio is 4.5 or more, can obtain stable fabulous luminosity.
Fig. 2 has shown the figure of the relation of electrogalvanizing steel plate (10.3) planar orientation index and brightness, the scope that it was fit to for (00.2) planar orientation index be 1.0 or more and (10.1) plane be 1.0 or few.When the orientation index scope of (10.3) crystal face is 2.0 or more, especially be 2.5 or more, steel plate shows and is not less than 80 high-level brightness, the only display brightness that is lower than 2.0 row is low to reach 65 or lower and those (10.3) planar orientation indexs belong to.
Fig. 3 illustrates electrogalvanizing steel plate [(00.2) and (10.3) planar orientation index and] and the ratio of [(10.1) planar orientation index] and the figure of the relation of luminosity, its scope that is fit to be (00.2) planar orientation index be suitable for 1.0 or more and (10.1) planar orientation index be 1.0 or still less.When above ratio is 4.5 or when higher, the high level brightness that steel plate shows is not less than 80, and those ratios belong to and are lower than 4.5 row, and steel plate only demonstrates and is not higher than 65 low-level brightness.
Can obviously find out from these results, be not less than 80 fabulous brightness by the L value in order to obtain to have, not only must control (00.2) planar orientation index to 1.0 or more some more and (10.1) planar to 1.0 or less, but also to control (10.3) planar to 2.0 or more some more, especially be 2.5 or higher, or the ratio to 4.5 of [(00.2) and (10.3) planar orientation index and] and [(10.1) planar orientation index] or higher.
In addition, the present inventor has carried out extensive investigations to each crystal face (hkl) of electric galvanizing coating and the relation of its brightness.The result, they successfully obtain unknown up to now newfound a kind of relation, promptly when with (00.2) plane being the basal plane of sexangle close-packed tissue of zinc during, the relation between brightness (L value) and each crystal face and the formed angle of basal plane [hereinafter will be called " index Plane Angle (deg) "] as basal plane.Index Plane Angle described above (deg) is displayed in Table 2 as follows.
Table 2
| (hkl) Miller indices plane | The index Plane Angle |
| (00.2) | 0 |
| (10.0) | 90 |
| (10.1) | 65 |
| (10.2) | 47 |
| (10.3) | 35.5 |
| (11.0) | 90 |
| (00.4) | 0 |
Under the situation of the zinc with sexangle packed structures, the index Plane Angle θ between two crystal faces is calculated as follows: each represents the constant and the (h of a lattice supposition a and c
1k
1L
1) and (h
2k
2L
2) represent crystal face (minute surface index plane), and θ (deg) represents the angle that forms between two crystal faces, and X, Y and Z are calculated by following equation separately,
X＝h
1×h
2+k
1×k
2+1/2(h
1×k
2+h
2×k
1)+
3/4(a/c)
2×(l
1×l
2)
Y＝h
1 2+k
1 2+(h
1×k
1)+3/4(a/c)
2×(l
1 2)
Z＝h
2 2+k
2 2+(h
2×k
2)+3/4(a/c)
2×(l
2 2)，
And the index Plane Angle between the crystal face is calculated by following corresponding equation:
cosθ＝X/(Y×Z)
1/2
Calculated value needs within 0-90 °.
The index Plane Angle of being determined by above equation (deg) is divided into two groups.One group is by (00.2), (10.3) and (00.4) three crystal face form, their index Plane Angle very little and within 0 to 35.5 ℃ and another group by (10.0), (10.1), (10.2) and (11.0) four crystal faces form, their index Plane Angle is very big.To the orientation index of each group and study with the relation of the luminosity on spelter coating surface, it is as follows to have produced the new discovery of also not being familiar with so far:
Specifically, have been found that when supposition Ico (hkl) represents orientation index of (hkl) crystal face and satisfied simultaneously relation of plane down
A＝[Ico(00·2)+Ico(00·4)+Ico(10·3)]≥8.0
B＝[Ico(10·0)+Ico(10·1)+Ico(10·2)+Ico(11·0)]≤1.0
Can guarantee to obtain the very electrogalvanizing steel plate of light degree.
Fig. 4 has shown the experimental result of their relation with the form of scheming.Can be clear that from figure the luminosity on surface that satisfies the electrogalvanizing steel plate of above two corresponding equation A and B simultaneously shows 80 the fabulous luminosity of being not less than with the L value representation.
The invention enables may be stable acquisition be not less than 80 electrogalvanizing steel plate with the brightness of L value representation, be higher than traditional steel plate brightness out and away, be not by stipulating each crystal face orientation index but by on seven planes (00.2), (10.3), (00.4), (10.0), (10.1), (10.2) control is as (00.2) of one group and in (11.0), (10.3)) and (00.4) planar orientation index and to 8.0 or more and control as (10.0) of another group, (10.1), (10.2) and (11.0) planar orientation index reaches 1.0 or still less.
By the way, the orientation index of crystal face is that each is self-corresponding, and does not have the relation of subordinate between them.When considering to belong to (00.2) that little finger of toe is counted one group of planar, (10.3) and during the orientation index of (00.4) three aspect, even one in these crystal faces [for example, (10.3) plane] orientation index be high (or low), the orientation index of two other crystal face (00.2) and (00.4) is not to uprise (or low) inevitably.This is applicable to one group (10.0) of big index Plane Angle too, (10.1), (10.2) and (11.0) four crystal faces.
The present invention is by introducing completely new concept, exactly, be categorized as two groups by crystal face, exactly one group of influence that luminosity is exerted and another group orientation index and the electrogalvanizing steel plate that obtains high brightness can be stable that luminosity is played opposite effect and specifies each group to electric galvanizing coating.
The present invention has carried out further investigation by the prerequisite that is categorized as described above.Its result, when except each group direction index and that belong to equation A and B that needs crystal face, their ratio (A/B) also should be at least 13.0, then can obtain outstanding high brightness; When (00.2) planar orientation index be 4.0 or more and (10.1) planar orientation index be 0.3 or fewer can obtain more stable high-level brightness.Therefore, this additional requirement is applied in the situation described above, then can obtains brightness value with the L value representation and be not less than 83 high brightness electrogalvanizing steel plate.
Fig. 5 simple displaying can satisfy the figure of the ratio of the A/B that equation A described above and B require to the influence of the brightness of electric galvanizing coating, when the ratio of A/B surpassed boundary line 13, brightness became very high and shows and is not less than 83 high L value.Fig. 6 simple displaying specifically those (00.2) and (10.1) planar orientation indexs of coating of requirement that can satisfy equation A and B to the influence of brightness.From this figure can recognize when (00.2) planar orientation index be 4.0 or more and simultaneously (10.1) plane be 0.3 or few, be preferably 0.2 or fewer the time can obtain 83 the high brightness of being not less than with the L value representation.
The determined concrete method that satisfies orientation index equation described above of the present invention is not forced special restriction, because various factors are depended in the variation of the orientation index of each crystal face, can not determine to satisfy the condition of whole equatioies, for example, in industrially scalable in the electro-galvanizing method of the employing acid bath generally used, consider that each planar orientation index then is subjected to the influence of variety of factors, as the coating current density, the continuous rising or the reduction of electric current, use the intermittence of electricity, the electric conductivity of plating bath, the pH value of plating bath, the kind and the concentration of impurity in the plating bath (organic or inorganic), relative velocity in the plating bath between the kind of additives and concentration and plating bath and the material plate, in order to satisfy the requirement of orientation index described above and relative equation, adopt control conditioned disjunction separately to control the method for some combination conditions.In the case, as the situation of considering the coating position initial experiment condition is set in advance and can guarantees enough reproducibilities.
As described above, the present invention is characterised in that the planar orientation index of (00.2) and (10.1) by specifying electric galvanizing coating and the ratio of (10.3) planar orientation index or [(0.02) and (10.3) planar orientation index with] and [(10.1) planar orientation index] simultaneously; Or one group orientation index by control equation A and to 8.0 or more and equation B to 1.0 or few, can obtain high-level brightness above traditional level.In addition, by specifying the A/B ratio also can obtain high brightness.Weight to the Zn coating does not have specific restriction.The coating wt of size often causes the reduction of erosion resistance, therefore needs the coating wt of control Zn to be preferably 3g/m
2Or more greatly, be preferably 20g/m
2Or more greatly.Owing to consider the raising of the spark expense that the raising of the weight of Zn coating causes, control the heavy upper limit of Zn coating usually and be preferably 100g/m
2Or few, 60g/m more preferably
2Or few, be preferably 40g/m
2Or it is few.
According to its purpose of using, may form the electric galvanizing coating of high brightness described above again at the one or both sides of steel plate.Also may form multilayered structure, and Ni coating such as Ni, Ni-Co or Ni-P; Zn coating such as Zn-Ni, Zn-Fe or Zn-Cr; Or Fe coating such as Fe-P and Fe-B have been applicable to undercoat.
The electrogalvanizing steel plate that very bright electric galvanizing coating is arranged among the present invention is because its fabulous brightness can commercialization.Also may carry out handling, further improve erosion resistance, formability, anti-impression of the hand and required performance like that the surface of steel plate as the chemical transformation of chromate coating or thin transparent organic or inorganic film coating.
Under above-mentioned situation, chemical transformation is handled or the following description of film coating processing meeting causes the slight minimizing of surface brightness, even but after such processing its L value be not less than 70, be significantly higher than traditional obtainable brightness of electric galvanizing coating steel plate.
Fig. 7 shows the figure of the weight and the relation between the luminosity of chromic acid coating.Luminosity produces slight reduction and when the weight increase of coating too many, the brightness meeting is reduced to the degree that can not be ignored when the increase of chromate coating weight.Even be not less than 75 high-level brightness in order to ensure L value behind chromate coating, the weight of Cr that needs the control chromate coating is to 50mg/m
2Or still less, 30mg/m preferably
2Or reduce.So little coating wt can not cause the increase of b value, and wherein the b value is used for measuring brightness color luminosity in addition, therefore can not cause the problem of the flavescence on surface.
The main purpose of chromate coating is the raising of anti-white rust spot (erosion resistance) that causes the surface of electric galvanizing coating.In order to reach this purpose, press the weight about 10 to 30mg/m of the coating of Cr
2Therefore be enough, need not be afraid of to lose its erosion resistance for fear of the reduction of brightness.
Method to chromate coating is not forced special restriction, can select arbitrary said chemical reaction type chromate coating, electrolytical chromium, chromate coatings and dry on the spot class chromate coating.In certain situation, they can be used in combination.In order further to improve erosion resistance, anti-scratch trace and anti-scales are used to add an amount of oxide compound such as silicon-dioxide, organosilane composition, and/or reaction accelerator such as phosphoric acid, and nitric acid, fluorochemical, the liquid chromate coating of silicofluoride also is effective.
Fig. 8 shows that thin transparent film coating on the chromate coating steel plate is to the influence of brightness.The reduction of recognizing brightness is owing to the transparent film coating.When the weight of transparent film coating surpasses 2g/m
2, can worry that the L value is lower than 70, i.e. the minimum index of brightness of the present invention.Therefore needing control transparent film coating wt is 2g/m by dry weight
2Or low, be preferably 1g/m
2Or it is low.The initial purpose of transparent film is to promote further to improve erosion resistance, the anti-impression of the hand of formability (lubrication) and generally speaking, at the transparent film coating wt 0.1 to 2g/m
2Left and right sides Shi Neng reaches this purpose fully.Therefore, need not pay close attention to for fear of the reduction of brightness and sacrifice the purpose and the performance of transparent film.When coating wt also need not fear to weaken conductivity and weldability during in above scope.
The constituent material that the transparent film coating is used is not forced special restriction.Most preferred embodiment comprises the formation agent that is used for transparent organic membrane, each all comprises a kind of organic resin of a kind of main component such as Resins, epoxy, vibrin, the polyurethane resin, ethylene copolymer resin, the unsaturated carboxylic acid that contains a kind of ethene of polymeric composition, polyvinyl resin, polyamide resin, acrylic resin or fluoro-resin, in addition as oxidosome for example silicon and phosphoric acid salt, the wax grain, the mineral dye of organosilane composition and/or naphthoate is used for further improving the erosion resistance lubricity, anti-scratch trace, formability, weldability, galvanic deposit, lacquer tack or like that, the formation agent of transparent organic membrane coating comprises a kind of phosphoric acid salt of a kind of main component such as sodium phosphate, potassiumphosphate or Trilithium phosphate in addition, add mineral dye such as oxidosome, as colloid silicon or phosphoric acid salt, wax grain and/or a kind of organic composite are with further raising film-forming properties, erosion resistance, oilness, electrodeposited coating performance and/or lacquer tack.They may be used alone, can also be used in combination.
The material of the steel plate that the present invention is used is not forced special restriction.Can use except that mild steel plate, high tensile steel plate and various alloy steel plate.
Embodiment
To more carefully describe the present invention by embodiment hereinafter but must clearly the invention is not restricted to following examples or limited, in not breaking away from main essential scope of the present invention, also may add change these embodiment by following examples.They are included in the present invention.
Embodiment
Electrogalvanizing steel plate is to adopt cold-rolled steel sheet to make according to program described below as the steel plate that carries out electro-galvanizing.The electro-galvanized steel plate portion forms chromate coating through chromic salt chemistry reaction treatment, forms the transparent film coating subsequently thereon.
(1) immerses aqueous basic solution surface degreasing: in 60 ℃ of weight percents are the aqueous solution of 3% sodium hydroxide, kept 2 minutes.
(2) in aqueous basic solution, use the electrolytic process surface degreasing: in 60 ℃ weight percents are the aqueous solution of 3% sodium hydroxide, kept 20A/dm 2 minutes
2
(3) wash
(4) pickling: with 40 ℃ weight percents is 5% aqueous sulfuric acid solution pickling 2 minutes.
(5) wash (6) electro-galvanizing
Electrolyzer-horizontal type
Bath composition: ZnSO
47H
2O 300 to 350 grams per liters
Na
2SO
450 to 100 grams per liters
H
2SO
43 to 30 grams per liters
Ni
2+0 to 200ppm
Fe
2+0 to 2000ppm
Sn
2+0 to 10ppm
In
2+0 to 200ppm
Pb
2+0 to 5ppm
Cu
2+0 to 1ppm
Electroplate density: 25 to 200A/dm
2
Bath temperature: 20,40,60 ℃ of flow velocitys: 1,2 meter per second
Electrode (anode): Pb alloy electrode coating wt: 20 gram/rice
2(each face)
(7) wash [following (8)-(10) are that some steel plates are carried out aftertreatment]
(8) chromate treating: chromic salt chemistry reaction treatment, press the coating wt of Cr: 10-100 milligram/rice
2
(9) wash
(10) thin organic-resin-film coating is handled:
Cross-linked polyethylene resin (additional colloid silicon and wax bits), coating wt: 0.5 to 5.0 gram/rice
2(be solid concentration by the conversion coating liquid, and the rotation frequency of coating equipment roller and pressure rolling pressure control coating weight)
(11) drying
The diffracted intensity of the X-ray diffraction of the electrogalvanizing steel plate that so obtains under following condition and each crystal face by spelter coating calculates its orientation index.In addition, the brightness of having measured the brightness value (L value) of electroplated coating (comprising chromate coating and thin organic membrane coated steel sheet) of acquisition like this and luminosity by as the criteria classification of following table 3 demonstrations.
Table 3
| Galvanized or zinc-plated and chromate coating material | Thin organic membrane coated material | Remarks (observation) | |
| A B C D | L value 〉=80 75≤L value＜80 65≤L value＜75 L value＜65 | L value 〉=80 70≤L value＜80 65≤L value＜70 L value＜65 | Very brilliant black is very black |
[condition of X-ray diffraction]
Diffractometer: the rotary anode type x-ray diffractometer, the product of Rigaku company limited,
Target: copper (causes unicolor by lacklustre monochromatic crystalline substance; Cu-Ka system)
X-ray tube voltage: 40 kilovolts of tube currents: 300 milliamperes
The angle of measuring: 30 to 80 ° of scanning speeds of 2 θ: 2 ° of/minute sample angle: 0.02 °
Disperse seam: 1 ° of scatter slit: 1 °
Light run through seam: 0.15 millimeter sample rotates in the plane: 100rpm
The results are shown in table 4-11.
Table 4: electrogalvanizing steel plate former state
| Numbering | The orientation index of crystal face | Chromate coating weight (mg/m 2) | Transparent film coating wt (mg/m 2) | The luminosity calculated value | Remarks | ||||
| (00·2) | (10·1) | (10·3) | X/Y | (L value) | |||||
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 | 1.50 1.39 2.02 1.54 1.50 1.84 1.75 1.08 0.88 * 1.53 1.08 1.18 1.56 2.02 1.89 1.53 0.20 * 0.49 * 0.90 * 0.65 * 0.21 * 0.55 * | 0.73 0.89 0.46 0.97 1.00 0.93 0.92 1.18 * 1.17 * 1.14 * 1.43 * 1.42 * 1.22 * 1.17 * 1.11 * 1.28 * 1.96 * 1.53 * 1.19 * 1.32 * 1.70 * 1.56 * | 3.01 2.89 2.11 1.27 * 0.96 * 0.82 * 1.90 * 2.13 2.12 1.41 * 0.67 * 0.57 * 0.70 * 0.25 * 0.98 * 0.57 * 0.76 * 1.02 * 1.93 * 1.69 * 0.57 * 1.38 * | 6.2 4.8 9.0 2.9 * 2.5 * 2.9 * 4.0 * 2.7 * 2.6 * 2.6 * 2.2 * 1.2 * 1.9 * 1.9 * 2.6 * 1.6 * 0.5 * 1.0 * 2.4 * 1.8 * 0.5 * 1.2 * | - - - - - - - - - - - - - - - - - - - - - - | - - - - - - - - - - - - - - - - - - - - - - | 84.0 82.6 85.0 55.8 51.5 49.9 60.2 66.0 77.1 47.1 72.2 74.1 70.0 66.2 57.5 67.5 64.1 73.1 78.8 78.2 65.9 63.9 | A A A D D D D C B D C C C C D C D C B B C D | Ex Ex Ex Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. |
Attention: X/Y=[(00.2) and (10.3) planar orientation index and]/(10.1) planar orientation index
*: outside specified scope
Table 5: through the electrogalvanizing steel plate of chromate coating processing
| Numbering | The orientation index of crystal face | Chromate coating weight (mg/m 2) | Transparent film coating wt (mg/m 2) | The brightness calculation value | Note | |||||
| (00·2) | (10·1) | (10·3) | X/Y | (L value) | ||||||
| 23 24 25 26 27 28 29 30 | 1.78 1.78 1.78 1.78 1.78 1.78 1.78 1.78 | 0.53 0.53 0.53 0.53 0.53 0.53 0.53 0.53 | 3.13 3.13 3.13 3.13 3.13 3.13 3.13 3.13 | 9.3 9.3 9.3 9.3 9.3 9.3 9.3 9.3 | - 10 15 20 30 50 70 100 | - - - - - - - - | 85.0 83.2 82.6 81.8 80.5 77.2 73.6 71.6 | A A A A A B C C | No. 23, No. 23 chromate coatings of No. 23 chromate coatings of No. 23 chromate coatings of No. 23 chromate coatings of No. 23 chromate coatings of No. 23 chromate coatings of chromate coating | Ex Ex Ex Ex Ex Ex Ref Ex Ref Ex |
Table 6 (Cont ' d): through the electrogalvanizing steel plate of thin organic membrane coating processing
| Numbering | The orientation index of crystal face | Chromate coating weight (mg/m 2) | Transparent film coating wt (mg/m 2) | The luminosity calculated value | Note | |||||
| (00·2) | (10·1) | (10·3) | X/Y | (L value) | ||||||
| 31 32 33 34 35 36 | 1.65 1.65 1.65 1.65 1.65 1.65 | 0.69 0.69 0.69 0.69 0.69 0.69 | 2.83 2.83 2.83 2.83 2.83 2.83 | 6.5 6.5 6.5 6.5 6.5 6.5 | - 20 20 20 20 20 | - - 0.2 0.3 0.5 0.7 | 83.9 82.4 78.7 76.8 76.0 74.6 | A A B B B B | No. 32 organic film coatings of No. 32 organic film coatings of No. 32 organic film coatings of No. 32 organic film coatings of No. 31 chromate coatings | Ex Ex Ex Ex Ex Ex |
Table 6
| Numbering | The orientation index of crystal face | Chromate coating weight (mg/m 2) | Transparent film coating wt (mg/m 2) | The luminosity calculated value | Note | |||||
| (00·2) | (10·1) | (10·3) | X/Y | (L value) | ||||||
| 37 38 39 40 41 | 1.65 1.65 1.65 1.65 1.65 | 0.69 0.69 0.69 0.69 0.69 | 2.83 2.83 2.83 2.83 2.83 | 65 6.5 6.5 6.5 6.5 | 20 20 20 20 20 | 1.0 1.5 2.0 3.0 5.0 | 73.4 72.2 70.7 68.3 64.8 | B B B C D | No. 32 organic film coatings of No. 32 organic film coatings of No. 32 organic film coatings of No. 32 organic film coatings of No. 32 organic film coatings | Ex. Ex. Ex. Ref Ex. Ref Ex. |
Table 7: electrogalvanizing steel plate former state
| Numbering | The orientation index of crystal face | Chromate coating weight (mg/m 2) | Transparent film coating wt (mg/m 2) | The luminosity calculated value | Note | ||||
| (00·2) | (10·1) | (10·3) | X/Y | (L value) | |||||
| 42 43 44 45 46 47 48 49 50 51 52 | 4.83 4.55 2.31 2.39 2.73 2.84 2.27 2.54 1.50 1.39 2.02 | 0.10 0.12 0.71 0.61 0.56 0.54 0.68 0.60 0.73 0.89 0.46 | 0.72 * 1.15 * 2.66 2.43 2.20 2.67 2.29 2.70 3.02 2.88 2.12 | 55.5 476. 7.0 7.9 8.8 10.2 6.7 8.9 6.2 4.8 9.0 | - - - - - - - - - - - | - - - - - - - - - - - | 86.0 85.6 82.0 83.8 82.5 83.9 81.2 82.0 83.0 82.6 85.0 | A A A A A A A A A A A | Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. |
Attention: X/Y=[(00.2) with (10.3) planar orientation index sum]/
(10.1) planar orientation index
Table 8: electrogalvanizing steel plate former state
| Numbering | The orientation index of crystal face | Chromate coating weight (mg/m 2) | Transparent film coating wt (mg/m 2) | The brightness calculation value | Note | |||
| Equation A | Equation B | A/B | (L value) | |||||
| 1 2 3 4 5 6 7 8 9 10 11 12 | 9.07 9.38 9.21 8.71 9.32 9.02 8.77 10.47 9.28 9.46 10.73 8.73 | 0.48 0.32 0.25 0.67 0.21 0.44 0.58 0.23 0.22 0.14 0.13 0.46 | 18.9 29.3 36.8 13.0 44.4 20.5 15.1 47.9 42.2 67.6 82.5 17.8 | - - - - - - - - - - - - | - - - - - - - - - - - - | 84.0 84.6 85.8 81.4 85.9 84.0 83.0 84.6 85.0 85.8 85.9 83.2 | A A A A A A A A A A A A | Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. |
Attention: equation A=[Ico (002)+Ico (004)+Ico (103)]
Equation B=[Ico (100)+Ico (101)+Ico (102)+Ico (110)]
Table 9: electrogalvanizing steel plate former state
| Numbering | The orientation index of crystal face | Chromate coating weight (mg/m 2) | Transparent film coating wt (mg/m 2) | The brightness calculation value | Note | |||
| Equation A | Equation B | A/B | (L value) | |||||
| 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 | 8.35 8.91 7.77 * 7.29 * 5.32 * 4.58 * 3.32 * 2.47 * 0.98 * 4.08 * 3.83 * 3.63 * 4.30 * 4.36 * 4.37 * | 1.17 * 1.25 * 1.12 * 1.32 * 1.50 * 1.77 * 2.67 * 3.04 * 4.15 * 2.62 * 2.75 * 2.77 * 2.41 * 3.08 * 2.07 * | 7.1 * 7.1 * 6.9 * 5.5 * 3.5 * 2.6 * 1.2 * 0.8 * 0.2 * 1.6 * 1.4 * 1.3 * 1.8 * 1.4 * 2.1 * | - - - - - - - - - - - - - - - | - - - - - - - - - - - - - - - | 77.1 76.0 75.3 74.5 72.1 69.2 68.1 64.4 64.9 67.6 69.9 65.7 66.2 50.3 57.3 | B B B C C C C D D C C C C D D | Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. |
Attention: equation A=[Ico (002)+Ico (004)+Ico (103)]
Equation B=[Ico (100)+Ico (101)+Ico (102)+Ico (110)]
*: numerical value is outside stated limit
Table 10: through the electrogalvanizing steel plate of chromate coating processing
| Numbering | The orientation index of crystal face | Chromate coating weight (mg/m 2) | Transparent film coating wt (mg/m 2) | The luminosity calculated value | Note | ||||
| Equation A | Equation B | A/B | (L value) | ||||||
| 28 29 30 31 32 33 34 35 | 9.46 9.46 9.46 9.46 9.46 9.46 9.46 9.46 | 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.14 | 67.6 67.6 67.6 67.6 67.6 67.6 67.6 67.6 | - 8 14 21 29 48 75 100 | - - - - - - | 85.9 83.9 82.8 82.3 81.0 77.7 74.9 71.5 | A A A A A B C C | No. 28 chromate coatings of No. 28 chromate coatings of No. 28 chromate coatings of No. 28 chromate coatings of No. 28 chromate coatings of No. 28 chromate coatings of No. 28 chromate coatings | Ex Ex Ex Ex Ex Ex Ref. Ex Ref. Ex |
Table 11: thin organic membrane coated material
| Numbering | The orientation index of crystal face | Chromate coating weight (mg/m 2) | Transparent film coating wt (mg/m 2) | The brightness calculation value | Note | ||||
| Equation A | Equation B | A/B | (L value) | ||||||
| 36 37 38 39 40 41 | 8.70 8.70 8.70 8.70 8.70 8.70 | 0.68 0.68 0.68 0.68 0.68 0.68 | 12.8 12.8 12.8 12.8 12.8 12.8 | - 21 21 21 21 21 | - - 0.2 0.3 0.5 0.7 | 81.8 81.0 77.0 76.1 74.8 74.2 | A A B B B B | No. 37 organic film coatings of No. 37 organic film coatings of No. 37 organic film coatings of No. 37 organic film coatings of No. 36 chromate coatings | Ex Ex Ex Ex. Ex. Ex. |
Table 11
| Numbering | The orientation index of crystal face | Chromate coating weight (mg/m 2) | Transparent film coating wt (mg/m 2) | The luminosity calculated value | Note | ||||
| Equation A | Equation B | A/B | (L value) | ||||||
| 42 43 44 45 46 | 8.70 8.70 8.70 8.70 8.70 | 0.68 0.68 0.68 0.68 0.68 | 12.8 12.8 12.8 12.8 12.8 | 21 21 21 21 21 | 1.0 1.5 2.0 3.0 4.5 | 73.6 72.7 71.2 68.4 65.0 | B B B C C | No. 37 organic film coatings of No. 37 organic film coatings of No. 37 organic film coatings of No. 37 organic film coatings of No. 37 organic film coatings | Ex. Ex. Ex. Ref Ex. Ref Ex. |
From table 4-7, can obtain following consideration:
(00.2) of the electric galvanizing coating that provides among the embodiment and two orientation indexs of (10.1) planar all satisfy needs of the present invention, and (10.3) planar orientation index satisfies the demands simultaneously; Or the ratio of [(00.2) and (10.3) planar orientation index and] and [(10.1) planar orientation index] satisfies the demands, when being the use of steel plate galvanized former state, maximum brightness is not less than 80 °, when being subjected to chromate coating, the steel surface is not less than 75, though each luminosity connects L value and found that slight brightness reduction also is not less than 70 when surface of steel plate stands thin transparent organic membrane coating.
Can find out significantly as the Nos.42 in the table 7 and 43, even (10.3) orientation index of face is less than 2.0, when [orientation index of (00.2) and (10.3) face and] and [ratio of the orientation index of (10.1) face] are 45 or when higher, can obtain the electrogalvanizing steel plate of high brightness.
On the other hand, at least one orientation index in three crystal faces of electric galvanizing coating can not satisfy specified demand, or the ratio of [(00.2) and (10.3) planar orientation exponential and] and [(10.1) planar orientation index] is darker luminosity specifying outside requiring without any the brightness of the electrogalvanizing steel plate of other coating.Especially, even (00.2) and (10.1) planar orientation index satisfy specified specific needs, when (10.3) planar orientation index specify to require outer or [(00.2) and (10.3) planar orientation index with] and the ratio of [(10.1) planar orientation index] can not satisfy specified requirement, luminosity without any the electric galvanizing coating of other coating shows tangible low-light level, and much less the electrogalvanizing steel plate of chromate coating and/or thin organic membrane coating has been arranged.
From table 8-11, can obtain following consideration:
When two values that calculated by equation A and B all meet the demands, electrogalvanizing steel plate in the embodiment of the invention has and is not less than 80 high brightness by the L value, chromium fourth salt coating is handled or thin transparent organic membrane coating is handled even electric galvanizing coating stands, still keep being not less than 70 high brightness, though there is slight brightness to reduce by the L value.
On the other hand, at least one value of equation A and equation B is outside above designated value in comparing embodiment, and it is 80 or higher high brightness that the electrogalvanizing steel plate of acquisition can not obtain by the L value.When chromate coating is pressed the weight raising of Cr and surpassed 50mg/m
2The time, after applying chromate coating, (with reference to embodiment 34,35) brightness value keeps 75 or higher, is appreciated that the degree for the brightness that keeps plan of the present invention, needs and will be compressed to 50mg/m by the chromate coating weight that Cr calculates
2, in reference embodiment (the 45th, No. 46), work as transparent organic membrane coating wt and exceed 2.0 gram/rice
2, brightness reduces a lot, and therefore in order to keep the L value to be not less than 70 after the transparent film coating, needing control transparent film coating wt is 2.0 gram/rice
2Or it is lower.
By the way, more than the orientation index that shows of table 8-11 and be that equation A and B by two crystal faces in electric galvanizing coating obtains.The orientation index of each crystal face relevant with some these coatings is presented at table 12 selectively.
Table 12
| Numbering | The orientation index of crystal face | Note | ||||||
| (00·2) | (10·0) | (10·1) | (10·2) | (10·3) | (11·0) | (00·4) | ||
| 1 5 7 9 | 4.21 4.96 4.37 5.05 | 0.00 0.07 0.06 0.07 | 0.16 0.05 0.19 0.05 | 0.32 0.07 0.29 0.10 | 1.52 0.42 0.93 0.21 | 0.00 0.02 0.04 0.00 | 3.34 3.94 3.47 4.02 | Example example example example |
| 13 16 21 26 | 3.14 3.16 0.21 1.55 | 0.00 0.13 0.89 0.29 | 0.45 0.47 1.70 0.97 | 0.67 0.72 0.47 0.81 | 1.87 1.61 0.57 1.27 | 0.05 0.00 1.09 1.01 | 3.34 2.52 0.20 1.54 | Comp.Ex. Comp.Ex. Comp.Ex. Comp.Ex. |
Claims (5)
1. the one or both sides of a steel plate all have the electrogalvanizing steel plate of the band brightness of electric galvanizing coating, it is characterized in that (00.2) plane of described electric galvanizing coating and (10.1) planar orientation index be respectively more than or equal to 1.0 and be less than or equal to 1.0 and simultaneously the ratio of [(00.2) and (10.3) planar orientation index sum] and [(10.1) planar orientation index] be more than or equal to 4.5, and on the described electric galvanizing coating surface formed chromate coating by Cr for being less than or equal to 50mg/m
2
2. according to the described electrogalvanizing steel plate of claim 1, the dry weight that it is characterized in that formed transparent film on the described chromate coating is for being less than or equal to 2 gram/rice
2
3. according to the described electrogalvanizing steel plate of claim 1, it is characterized in that the brightness (L value) of wherein measuring by JISI 8730 is at least 80.
4. according to the described electrogalvanizing steel plate of claim 1, it is characterized in that the brightness (L value) of wherein measuring by JISZ 8730 is at least 75.
5. according to the described electrogalvanizing steel plate of claim 2, it is characterized in that the brightness (L value) of wherein measuring by JISZ 8730 is at least 70.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP170122/1996 | 1996-06-28 | ||
| JP17012396A JP2831975B2 (en) | 1996-06-28 | 1996-06-28 | Electro-galvanized steel sheet |
| JP170123/96 | 1996-06-28 | ||
| JP17012296A JP3363033B2 (en) | 1996-06-28 | 1996-06-28 | Electro-galvanized steel sheet |
| JP170123/1996 | 1996-06-28 | ||
| JP170122/96 | 1996-06-28 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1173551A CN1173551A (en) | 1998-02-18 |
| CN1166815C true CN1166815C (en) | 2004-09-15 |
Family
ID=26493216
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB971125732A Expired - Lifetime CN1166815C (en) | 1996-06-28 | 1997-06-26 | Electrogalvanized steel sheet with light tone |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR100235918B1 (en) |
| CN (1) | CN1166815C (en) |
| ID (1) | ID18574A (en) |
| TW (1) | TW448244B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5130080B2 (en) | 2008-02-29 | 2013-01-30 | 株式会社神戸製鋼所 | Phosphate-treated electrogalvanized steel sheet |
| KR101860071B1 (en) * | 2009-11-20 | 2018-06-27 | 도요 고한 가부시키가이샤 | Method for manufacturing surface-treated steel sheet for cover member |
-
1997
- 1997-06-06 TW TW086107838A patent/TW448244B/en not_active IP Right Cessation
- 1997-06-21 KR KR1019970026387A patent/KR100235918B1/en not_active IP Right Cessation
- 1997-06-26 CN CNB971125732A patent/CN1166815C/en not_active Expired - Lifetime
- 1997-06-30 ID IDP972285A patent/ID18574A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| ID18574A (en) | 1998-04-23 |
| TW448244B (en) | 2001-08-01 |
| KR980002305A (en) | 1998-03-30 |
| KR100235918B1 (en) | 1999-12-15 |
| CN1173551A (en) | 1998-02-18 |
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